US20230303768A1 - High-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether and preparation method - Google Patents
High-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether and preparation method Download PDFInfo
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 106
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 14
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 18
- 229920000570 polyether Polymers 0.000 abstract description 18
- 238000007670 refining Methods 0.000 abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2687—Elements not covered by groups C08G65/2672 - C08G65/2684 or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2693—Supported catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention belongs to the technical field of organic high-molecular compounds, in particular to a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether and a preparation method.
- An allyl alcohol polyoxyethylene polyoxypropylene ether is an unsaturated polyether of which one end is an allyl group and the other end is a hydroxyl group, and its double bond may be used to react with various active groups so as to introduce the special properties such as the lubricating effect, softening effect, demulsibility and defoaming property provided by a polyether chain segment into various new-type multi-functional fine chemical products.
- a two-step method is often used in the existing industry to prepare an allyl alcohol polyoxyethylene polyoxypropylene random polyether. Namely, Na, K or its hydroxides or a sodium methoxide, a potassium methoxide or the like is used as a catalyst, a low-molecular weight allyl alcohol random polyether 400-1500 is firstly synthesized, then the low-molecular weight random polyether is used as a starting agent, and a mixture of an ethylene oxide and a propylene oxide is used as a chain extender, to synthesize the high-molecular weight allyl alcohol random polyether.
- a patent CN102911352B prepares the allyl alcohol random polyether by refining according to this method, and its disadvantage is that while the molecular weight of the allyl alcohol random polyether is increased to a certain amount (>3000), the product filtering speed is extremely slow, so that the production cycle becomes longer, the profit is reduced, and a large number of adsorbent waste residues may be generated after filtering, these waste adsorbents are bound to cause the resource waste and produce the secondary pollution.
- a purpose of the present invention is to provide a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether which may omit the refining process of a polyether, greatly simplify the process flow, and effectively save the process time, and the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether prepared by this method.
- the present invention provides a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, including:
- reaction mechanism of the preparation method is as follows.
- the supported catalyst Rb-NHPA in the step S 1 is prepared by the following steps.
- the mass ratio of the NHPA support to the deionized water is 0.5 ⁇ 2:3.
- step S 1 - 1 operations of “performing the water vapor pore expansion treatment of the NHPA support under the condition of gas protection, and after vacuum-drying and removing the water, roasting, cooling, and vacuumizing” are specifically as follows: under the conditions of 120° C. of the temperature, 1.2 Mpa of the pressure, and using N 2 as a protective gas, after performing the water vapor pore expansion treatment on the NHPA support for 2 h, putting it into a 110° C. vacuum drying oven and drying for 6 h, to remove the water, then roasting in a 600° C. muffle furnace for 4 h, and vacuumizing for 30 min after cooling to a room temperature.
- step S 1 - 2 after the rubidium hydroxide solution is added, it is intensely stirred for 6 ⁇ 8 hours at 60° C. ⁇ 80° C., and the intermittent ultrasonic assisted impregnation is performed for two times, and after being filtered, it is put into a 120° C. vacuum drying oven and dried for 12 h, after the porous honeycomb solid is formed, it is roasted for 3 h at 600° C.
- the amount of the supported catalyst Rb-NHPA in the S 1 is 0.05% ⁇ 0.5% of the mass of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether obtained finally.
- the molecular weight of the obtained crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is 3000-8000, and the weight ratio of EO to PO in the S 2 is 1:0.5 ⁇ 5.
- reaction temperature of the step S 2 may be 80° C. ⁇ 150° C., and the reaction pressure thereof is ⁇ 0.09 ⁇ 0.40 Mpa; and in the step S 3 , the internal temperature of the reaction kettle is reduced to 50° C., and the stirring time is 30 ⁇ 60 minutes.
- the present invention further provides a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, and it is prepared by the above preparation method for the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether.
- FIG. 1 is a flow schematic diagram of a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether of the present invention.
- FIG. 2 is a preparation flow schematic diagram of a supported catalyst Rb-NHPA in the preparation method for the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether of the present invention.
- the present invention provides a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, including the following steps.
- the supported catalyst Rb-NHPA is a porous honeycomb solid catalyst formed by using NHPA as a support and supporting alkali metal rubidium (Rb), and the specific preparation steps are shown in FIG. 2 , including:
- the reaction mechanism of the preparation method is as follows.
- a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is specifically prepared by using the following steps.
- Embodiments 2-5 and Embodiment 1 A difference between Embodiments 2-5 and Embodiment 1 is only that the masses of the allyl alcohol, the supported catalyst Rb-NHPA, EO and PO are different, and it is specifically shown in Table 1 below.
- Contrast examples 2-5 and Contrast example 1 A difference between Contrast examples 2-5 and Contrast example 1 is only that the masses of the allyl alcohol random polyether 900, KOH, EO and PO are different, and it is specifically shown in Table 2 below.
- Hydroxyl value determined according to a phthalic anhydride method in GB/T 7383-2007.
- Iodine value determined according to GB/T 13892-2012.
- the double bond retention rate is calculated according to the following formula,
- I (M hydroxyl value/M iodine value)*100%, herein I is the double bond retention rate, M hydroxyl value is the molecular weight calculated by the hydroxyl value, and M iodine value is the molecular weight calculated by the iodine value.
- a gel permeation chromatography uses a chromatographic pure tetrahydrofuran as a mobile phase, the preparation concentration is 0.01 g/mL, and the test temperature is 40° C.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Polyethers (AREA)
Abstract
Description
- The present application claims priority from Chinese Patent Application No. 202210310861.4 filed on Mar. 28, 2022, the contents of which are incorporated herein by reference in their entirety.
- The present invention belongs to the technical field of organic high-molecular compounds, in particular to a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether and a preparation method.
- An allyl alcohol polyoxyethylene polyoxypropylene ether is an unsaturated polyether of which one end is an allyl group and the other end is a hydroxyl group, and its double bond may be used to react with various active groups so as to introduce the special properties such as the lubricating effect, softening effect, demulsibility and defoaming property provided by a polyether chain segment into various new-type multi-functional fine chemical products.
- However, it is found by the applicant that: a two-step method is often used in the existing industry to prepare an allyl alcohol polyoxyethylene polyoxypropylene random polyether. Namely, Na, K or its hydroxides or a sodium methoxide, a potassium methoxide or the like is used as a catalyst, a low-molecular weight allyl alcohol random polyether 400-1500 is firstly synthesized, then the low-molecular weight random polyether is used as a starting agent, and a mixture of an ethylene oxide and a propylene oxide is used as a chain extender, to synthesize the high-molecular weight allyl alcohol random polyether. A prepared crude product of the allyl alcohol random polyether needs to remove residual alkali metal ions in the product by a complicated post-treatment process so that a reaction of a subsequent product is not affected, and in the post-treatment process, deionized water needs to be added to dissociate the alkali metals, a phosphoric acid is added for neutralization, an adsorbent such as a silicate is used for adsorption, and after co-heated dehydration, it is filtered to remove the alkali metal ions and acid radical ions in the product. A patent CN102911352B prepares the allyl alcohol random polyether by refining according to this method, and its disadvantage is that while the molecular weight of the allyl alcohol random polyether is increased to a certain amount (>3000), the product filtering speed is extremely slow, so that the production cycle becomes longer, the profit is reduced, and a large number of adsorbent waste residues may be generated after filtering, these waste adsorbents are bound to cause the resource waste and produce the secondary pollution.
- In order to overcome deficiencies of an existing technology, a purpose of the present invention is to provide a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether which may omit the refining process of a polyether, greatly simplify the process flow, and effectively save the process time, and the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether prepared by this method.
- In order to solve the above problems, technical schemes adopted by the present invention are as follows.
- The present invention provides a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, including:
-
- S1, adding an allyl alcohol raw material and a supported catalyst Rb-NHPA into a high-pressure reaction kettle, and heating after the interior of the reaction kettle is replaced with a nitrogen gas;
- S2, after the internal temperature of the reaction kettle is raised to a reaction temperature, continuously feeding an ethylene oxide (EO) and propylene oxide (PO) mixture for a reaction, and after the mixture is added, maturing until the internal pressure of the reaction kettle is no longer decreased, stopping the reaction, and removing a low-boiling point substance in vacuum, to obtain a crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether; and
- S3, after the internal temperature of the reaction kettle is reduced, dropwise adding an acetic acid into the reaction kettle so that the crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is neutralized to be neutral, stirring, and filtering, to obtain the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether.
- Further, the reaction mechanism of the preparation method is as follows.
- Further, the supported catalyst Rb-NHPA in the step S1 is prepared by the following steps.
-
- S1-1, hydrothermal pore expansion pretreatment of support: putting a nano-hydroxyapatite (NHPA) support into the reaction kettle, adding deionized water, and performing water vapor pore expansion treatment of the NHPA support under a condition of gas protection, and after vacuum-drying and removing the water, roasting, cooling, and vacuumizing.
- S1-2, equivalent-volume impregnation: dissolving the NHPA support after the hydrothermal pore expansion pretreatment in anhydrous ethanol, adding rubidium hydroxide solution and stirring intensely, so that the NHPA support is fully contacted with an active component, then filtering after intermittent ultrasonic assisted impregnation, vacuum-drying, to form a porous honeycomb solid, and roasting, to obtain the supported catalyst Rb-NHPA.
- Further, the mass ratio of the NHPA support to the deionized water is 0.5˜2:3.
- Further, the mass ratio of the rubidium hydroxide solution to the anhydrous ethanol is 0.5˜5:10.
- Further, in the step S1-1, operations of “performing the water vapor pore expansion treatment of the NHPA support under the condition of gas protection, and after vacuum-drying and removing the water, roasting, cooling, and vacuumizing” are specifically as follows: under the conditions of 120° C. of the temperature, 1.2 Mpa of the pressure, and using N2 as a protective gas, after performing the water vapor pore expansion treatment on the NHPA support for 2 h, putting it into a 110° C. vacuum drying oven and drying for 6 h, to remove the water, then roasting in a 600° C. muffle furnace for 4 h, and vacuumizing for 30 min after cooling to a room temperature.
- Further, in the step S1-2, after the rubidium hydroxide solution is added, it is intensely stirred for 6˜8 hours at 60° C.˜80° C., and the intermittent ultrasonic assisted impregnation is performed for two times, and after being filtered, it is put into a 120° C. vacuum drying oven and dried for 12 h, after the porous honeycomb solid is formed, it is roasted for 3 h at 600° C.
- Further, the amount of the supported catalyst Rb-NHPA in the S1 is 0.05%˜0.5% of the mass of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether obtained finally.
- Further, the molecular weight of the obtained crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is 3000-8000, and the weight ratio of EO to PO in the S2 is 1:0.5˜5.
- Further, the reaction temperature of the step S2 may be 80° C.˜150° C., and the reaction pressure thereof is −0.09˜0.40 Mpa; and in the step S3, the internal temperature of the reaction kettle is reduced to 50° C., and the stirring time is 30˜60 minutes.
- The present invention further provides a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, and it is prepared by the above preparation method for the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether.
- Compared with the existing technology, the beneficial effects of the present invention are as follows.
- The present invention adopts the supported catalyst Rb-NHPA with high activity, so that the reaction is more complete and more sufficient. Under the condition of the same molecular weight, the double bond retention rate is high, the distribution coefficient is small, the reaction time is shorter, and the by-product content is low, so the refining process of the polyether is omitted, and the process time is greatly saved. In addition, the supported catalyst Rb-NHPA may be recycled, reused, and environment-friendly, and the cost may also be reduced.
-
FIG. 1 is a flow schematic diagram of a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether of the present invention. -
FIG. 2 is a preparation flow schematic diagram of a supported catalyst Rb-NHPA in the preparation method for the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether of the present invention. - In order to make purposes, technical schemes and advantages of the present invention more clear, the present invention is further described in detail below in combination with drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, not to limit the present invention.
- Referring to
FIG. 1 , the present invention provides a preparation method for a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, including the following steps. -
- Step S100, an allyl alcohol raw material and a supported catalyst Rb-NHPA are added into a high-pressure reaction kettle, and it is heated after the interior of the reaction kettle is replaced with a nitrogen gas; and herein, the amount of the supported catalyst Rb-NHPA is 0.05%˜0.5% of the mass of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether obtained finally.
- The supported catalyst Rb-NHPA is a porous honeycomb solid catalyst formed by using NHPA as a support and supporting alkali metal rubidium (Rb), and the specific preparation steps are shown in
FIG. 2 , including: -
- Step S101, hydrothermal pore expansion pretreatment of support: the NHPA support is put into the reaction kettle, deionized water is added, and water vapor pore expansion treatment of the NHPA support is performed under a condition of gas protection, and after vacuum-drying is performed and the water is removed, it is roasted, cooled, and vacuumized. It is specifically as follows: under the conditions of 120° C. of the temperature, 1.2 Mpa of the pressure, and using N2 as a protective gas, after the water vapor pore expansion treatment is performed on the NHPA support for 2 h, it is put into a 110° C. vacuum drying oven and dried for 6 h, to remove the water, then it is roasted in a 600° C. muffle furnace for 4 h, and vacuumized for 30 min after being cooled to a room temperature.
- Step S102, equivalent-volume impregnation: the NHPA support after the hydrothermal pore expansion pretreatment is dissolved in anhydrous ethanol, rubidium hydroxide solution is added and stirred intensely (preferably it is stirred intensely at 60° C.˜80° C. for 6-8 hours), so that the NHPA support is fully contacted with an active component, then it is filtered after intermittent ultrasonic assisted impregnation (preferably the intermittent ultrasonic assisted impregnation is performed for two times), and vacuum-dried, to form a porous honeycomb solid, and it is roasted (preferably it is roasted at 600° C. for 3 hours), to obtain the supported catalyst Rb-NHPA.
- Step S200, after the internal temperature of the reaction kettle is raised to a reaction temperature, an EO and PO mixture is continuously fed into the reaction kettle for a reaction, and after the mixture is added, it is matured until the internal pressure of the reaction kettle is no longer decreased, the reaction is stopped, and a low-boiling point substance (the low-boiling point substance is an incompletely reacted EO and PO mixture and an aldehyde low-boiling point substance generated by a side reaction) is removed in vacuum, to obtain a crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether; and herein, the weight ratio of EO to PO is 1:0.5˜5, and the molecular weight of the obtained crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is 3000˜8000.
- Step S300, after the internal temperature of the reaction kettle is reduced, an acetic acid is dropwise added into the reaction kettle so that the crude product of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is neutralized to be neutral, and it is stirred, and filtered, to obtain the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether.
- The reaction mechanism of the preparation method is as follows.
- Compared with the existing technology, the preparation method of the present invention uses the supported catalyst Rb-NHPA with high activity, so that the reaction is more complete and more sufficient. Under the condition of the same molecular weight, the double bond retention rate is high, the distribution coefficient is small, the reaction time is shorter, and the by-product content is low, so the refining process of the polyether is omitted, and the process time is greatly saved. In addition, the supported catalyst Rb-NHPA may be recycled, reused, and environment-friendly, and the cost may also be reduced.
- The high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether and the preparation method of the present invention are further described below by embodiments and contrast examples.
- In Embodiment 1, a high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is specifically prepared by using the following steps.
-
- S1: 33.1 g of anhydrous allyl alcohol and 9.15 g of a supported catalyst Rb-NHPA are added into a reaction kettle, and it is heated after the interior of the reaction kettle is replaced with a nitrogen gas.
- S2: while the temperature is raised to about 80-85° C., 1082 g of EO and 885 g of PO are simultaneously fed into the reaction kettle, and after EO and PO are added, feeding is stopped, it is matured for a certain time, and while the pressure is no longer decreased, it is vacuum-degassed, and cooled.
- S3: while the reaction temperature is reduced to about 50° C., 6.4 g of an acetic acid is dropwise added into the reaction kettle, and it is filtered after being stirred for 30 min, and discharged, to obtain the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether, and the supported catalyst Rb-NHPA is recovered.
- A difference between Embodiments 2-5 and Embodiment 1 is only that the masses of the allyl alcohol, the supported catalyst Rb-NHPA, EO and PO are different, and it is specifically shown in Table 1 below.
-
TABLE 1 Allyl Acetic Embodiment alcohol Rb-NHPA EO PO acid 1 33.1 9.15 1082 885 6.4 2 25.8 9.15 1086 888 6.4 3 21.1 9.15 1088 878 6.4 4 17.8 9.15 1090 876 6.4 5 15.4 9.15 1092 874 6.4 - A high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether is prepared by an existing technology, and a specific process is as follows.
- S1: 96.6 g of anhydrous allyl alcohol and 4.5 g of a potassium hydroxide are added into a reaction kettle, and it is heated after the interior of the reaction kettle is replaced with N2.
-
- S2: while the temperature is raised to 80-85° C., 772 g of EO and 631 g of PO are simultaneously fed into the reaction kettle, and after EO and PO are added, feeding is stopped, it is matured for a certain time, and while the pressure is no longer decreased, it is vacuum-degassed, cooled, and discharged, to obtain an intermediate allyl alcohol random polyether 900.
- S3: after the reaction kettle is cleaned and dried, 514 g of the intermediate allyl alcohol random polyether 900 and 4.5 g of the potassium hydroxide (KOH) are added into the reaction kettle, and the temperature is raised after the interior of the reaction kettle is replaced with N2.
- S4: after the temperature is raised to 105-115° C., it is dehydrated for 1 h, and after that, 817 g of EO and 669 g of PO are continuously fed into the reaction kettle, after EO and PO are added, it is matured for a certain time, and while the pressure in the reaction is no longer decreased, it is degassed, and cooled below 50° C.
- S5: 140 g of deionized water and 10.5 g of a phosphoric acid are added into the reaction kettle, it is stirred for 15 min, 30.0 g of a polyether adsorbent aluminum silicate is added, it is continuously stirred for 30 min, then the temperature is raised to 80-85° C. and it is vacuum-dehydrated, and after dehydration, the temperature is continuously raised to 110-120° C. and kept for 1 h, after that, it is cooled, and filtered, to obtain the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether.
- A difference between Contrast examples 2-5 and Contrast example 1 is only that the masses of the allyl alcohol random polyether 900, KOH, EO and PO are different, and it is specifically shown in Table 2 below.
-
TABLE 2 Allyl alcohol random Deion- Phos- Contrast polyether ized phoric Aluminum example 900 KOH EO PO water acid silicate 1 514 4.5 817 669 140 10.5 30.0 2 400 4.8 880 720 140 10.5 30.0 3 327 5.0 920 753 140 10.5 30.0 4 276 5.2 948 776 140 10.5 30.0 5 240 5.3 968 792 1400 10.5 30.0 - The high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ethers prepared in Embodiments 1-5 and Contrast examples 1-5 are characterized, and a testing method is as follows.
- Hydroxyl value: determined according to a phthalic anhydride method in GB/T 7383-2007.
- Iodine value: determined according to GB/T 13892-2012.
- The double bond retention rate is calculated according to the following formula,
- I=(M hydroxyl value/M iodine value)*100%, herein I is the double bond retention rate, M hydroxyl value is the molecular weight calculated by the hydroxyl value, and M iodine value is the molecular weight calculated by the iodine value.
- A gel permeation chromatography (GPC) uses a chromatographic pure tetrahydrofuran as a mobile phase, the preparation concentration is 0.01 g/mL, and the test temperature is 40° C.
- Test results are shown in Table 3 below.
-
TABLE 3 Iodine Double Number Molecular Hydroxyl value bond average weight value (gI2/ retention molecular distribution (mgKOH/g) 100 g) rate (/%) weight coefficient Embodiment 16.5 7.6 97.9 3378 1.05 1 Contrast 17.5 7.8 96.1 3226 1.07 example 1 Embodiment 13.6 6.0 97.3 4297 1.06 2 Contrast 14.1 6.2 95.9 4101 1.09 example 2 Embodiment 11.2 4.9 96.2 5205 1.07 3 Contrast 12.1 5.2 94.3 4880 1.11 example 3 Embodiment 9.5 4.1 95.7 6134 1.09 4 Contrast 10.4 4.5 93.7 5625 1.16 example 4 Embodiment 8.4 3.6 95.1 7054 1.10 5 Contrast 9.4 4.0 92.5 6362 1.18 example 5 - It may be seen from the experimental results that while the molecular weight design of the high-molecular weight allyl alcohol polyoxyethylene polyoxypropylene ether prepared by the method provided by the present invention is the same, the double bond retention rate is high and the distribution coefficient is small, this is because the supported catalyst Rb-NHPA has the higher catalytic activity, the reaction is more complete relatively, the reaction time is shorter, and the by-product content is low; compared with the existing process, the supported catalyst may be recycled and reused; and because the post-treatment process is not required, the process time is greatly saved, and the waste adsorbent does not need to be treated, it is environment-friendly.
- The above implementation modes are only preferred implementation modes of the present invention, and may not be used to limit a scope of protection of the present invention. Any non-substantial changes and replacements made by those skilled in the art on the basis of the present invention belong to the scope of protection claimed by the present invention.
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